Electrochemical Behavior of Thiocarbonylthio Chain Transfer Agents for RAFT Polymerization

Lisa T. Strover, Alexis Cantalice, Jeff Y.L. Lam, Almar Postma, Oliver E. Hutt, Michael D. Horne, Graeme Moad

Research output: Contribution to journalArticlepeer-review

28 Scopus citations


Electrochemical activation of thiocarbonylthio reversible addition-fragmentation chain transfer (RAFT) agents (S=C(Z)S-R) is explored as a potential method for initiating RAFT polymerization under mild conditions without producing initiator-derived byproducts. Herein we apply cyclic voltammetry to establish a predominant reduction mechanism, where electrochemical reduction is coupled to an irreversible first-order chemical reaction. Structure-dependent trends in cyclic voltammograms (CVs), and comparison to absorption spectra, clarify the role of R- A nd Z-groups in determining reduction processes. The major reduction peak moves to more cathodic potentials in the series dithiobenzoates > trithiocarbonates > heteroaromatic dithiocarbamates > xanthates ∼N-alkyl-N-aryldithiocarbamates, due to the Z-group influence on thiocarbonyl bond reactivity. More active (electron-withdrawing, radical stabilizing) R-groups shift the reduction peak anodically, in part due to their influence on the rate of the coupled chemical reaction. Analysis of CVs across a range of scan rates revealed that kinetic control over the reduction mechanism is influenced by both the charge transfer rate and chemical reaction rate.

Original languageEnglish
Pages (from-to)1316-1322
Number of pages7
JournalACS Macro Letters
Issue number10
StatePublished - 15 Oct 2019
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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